β-Sulfenyl acrylic acid compounds and process of preparing same

ABSTRACT

Compounds having the formula ##STR1## wherein R 1  is alkyl having 1 to 20 carbon atoms, preferably 6 to 20 carbon atoms, and R 3  and R 4  are hydrogen, alkyl having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms, or substituted alkyl having 2 to 6 carbon atoms and substituted by hydroxyl or sulfo salt. The compounds are prepared by reacting R&#39;SH with acetylene monocarboxylic acid and then reacting the thus-formed intermediate with an amine. The compounds possess surface active and antibiotic properties.

CROSS REFERENCE TO RELATED APPLICATION

This is a continuation-in-part of U.S. patent application Ser. No. 699,324, filed June 24, 1976, now abandoned.

The present invention relates to β-sulfenyl acrylic acid amides and a method of preparing those compounds.

Many problems arise when conventional antibiotic chemicals are used. A primary problem is that each of the known antibiotic chemicals can only be applied to a small group of systems or species of micro-organisms. Under the present circumstances, it is therefore necessary to subject to various tests a number of available antibiotic chemicals in order to select a specific chemical which is suited for applying to the particular system or specie. Although the antibiotic chemicals of the phenol system have been widely used, this kind of chemical, in general, has only a narrow spectrum of antibiotic activity and it must be used at a high concentration. Antibiotic chemicals of the halogen-substituted aromatic compound system, which is a different kind of widely used antibiotic chemical, tend to be accumulated in the natural world without being decomposed, and this can cause another kind of problem. It is also known that invert soaps exhibit remarkable antibiotic activities at low concentations. However, it is difficult to apply invert soaps to a system in which it is desired to reduce lathering of the soaps or to an anionic emulsion system, because the invert soaps form insoluble complexes with such systems.

The present invention has been developed after our strenuous efforts to solve the aforementioned problems.

The present invention provides β-sulfenyl acrylic acid and derivatives thereof which have the following formula (1), and method of preparing such compounds. ##STR2##

In the above formula (1), R¹ is alkyl having 1 to 20 carbon atoms, preferably from 6 to 20 carbon atoms and, most preferably, from 8 to 12 carbon atoms, R³ and R₄, which can be the same or different, are hydrogen, unsubstituted alkyl having 1 to 20 carbon atoms, especially from 1 to 6 carbon atoms, or substituted alkyl having 2 to 6 carbon atoms and having a substituent selected from the group consisting of hydroxyl and a sulfo group in a form of a salt (--SO₃ M), wherein M is an alkali metal.

β-SULFENYL ACRYLIC ACID AND SALTS THEREOF HAVING THE FORMULA (2):

    R.sup.1 S--CH═CH--COOM                                 (2)

wherein R¹ is the same as in the formula (1) and M is hydrogen or an alkali metal, are prepared by reacting mercaptans having the formula (3):

    R.sup.1 SH                                                 (3)

with acetylene monocarboxylic acid in an aqueous solution in the presence of an alkali metal hydroxide.

A reaction in which p-tolyl mercaptan is added to acetylene monocarboxylic acid using sodium ethoxide catalyst in ethanol is known in the art (W. E. Twce, D. L. Goldhamer & R. B. Kwse, J. Amer. Chem. Soc., vol. 81, page 4931 (1959)).

We have found that the addition reaction at the molar ratio of 1:1 between a mercaptan of the formula (3) and acetylene monocarboxylic acid takes place in an aqueous solution thereof, in the presence of a catalyst of an alkali metal hydroxide with increased yields of the desired products.

In the present invention, the mol ratio of mercaptan to acetylene monocarboxylic acid is 1:1.0 to 1.3. It is not preferred to employ an amount of acetylene monocarboxylic acid less than the above noted range, because unreacted mercaptan remains. The reaction temperature is maintained generally within the range of 0° to 100° C., preferably from 20° to 60° C. The preferred catalysts are sodium hydroxide and potassium hydroxide.

Halides of β-sulfenyl acrylic acid having the formula:

    R.sup.1 S--CH═CH--COY                                  (4)

wherein R¹ is the same as defined above, and Y is halogen, are prepared by reacting β-sulfenyl acrylic acid with halides of inorganic acids.

Examples of halides of inorganic acids are thionyl chloride (SOCl₂), phosphorus trichloride (PCl₃), phosphorus pentachloride (PCl₅), phosphorus oxychloride (POCl₃), phosphorus tribromide (PBr₃) and phosphorus pentabromide (PBr₅).

It is preferred to employ about 1.3 to 2 mols of the inorganic acid halide per one mole of β-sulfenyl acrylic acid, in the method of the present invention.

The reaction is carried out at a reaction temperature of 0° to 70° C. generally for from 30 minutes to 4 hours. For example, a preferred reaction time period at 0° C. is 1 to 4 hours, and at 70° C. is 30 minutes to 2 hours.

A solvent may or may not be used as a reaction medium. The preferred solvents are halogenated hydrocarbon solvents such as CCl₄, CHCl₃ and CH₂ Cl₂.

β-sulfenyl acrylic amides having the above formula (1) can be prepared by reacting β-sulfenyl acrylic acid or halides thereof with one or more of primary or secondary amines having the formula (4):

    HNR.sup.3 R.sup.4                                          ( 5)

wherein R³ and R⁴ have the same meaning as defined above.

There are two methods for preparing such amides.

(1) A method which comprises heating to remove water from the reaction mixture which contains β-sulfenyl acrylic acid and one or more of the amines and which does not contain any solvent.

(2) A method which comprises reacting a halide of β-sulfenyl acrylic acid with one or more of the amines, in a basic solvent such as an aqueous solution of sodium hydroxide or sodium carbonate or pyridine.

In the method (1), the yield of the formed amide of the formula (1) will be increased if more than 2 mols of amines are used per 1 mol of the used acid. The generally preferred reaction temperature is 150° to 170° C., and the reaction mixture is heated until about 1 mol of water is distilled off.

In the method (2), 2 to 3 mols of amines are used per 1 mol of the used acid halide, and the reaction is allowed to proceed generally at 0° to 50° C.

Beta-sulfenyl acrylic acid per se, and derivatives thereof, according to the present invention, which are represented by the above formula (1) and the compounds represented by the formula of R¹ SO_(n) --CH═CH--CONR³ R⁴ (wherein R¹, R³ and R⁴ are the same as described hereinabove and n=1 or 2) which are obtainable by oxidizing the compounds of formula (1) with an organic or inorganic peroxide, have surface active properties and antibiotic functions and they can be used as detergents, germicides, disinfectants and the like.

The antibiotic activities of the individual compounds of the present invention differ from each other due to the differences in their structure, so that the compounds of the present invention with different atoms or groups as R¹, R³ and R⁴ have, inclusively, a wide range of antibiotic activities and are effective against a wide range of microorganisms.

β-sulfenyl acrylic amides having the formula (1) can be effectively used as dispersing agents, germicides, antifungal agents or antiseptics in cosmetic goods and mixcellaneous products for domestic use.

The present invention will be further described in more detail with reference to illustrative Examples thereof. In the Table showing the results of the antibiotic properties, there will be shown the antibiotic properties of the compounds which are obtained by oxidizing the compounds of the present invention and which are represented by the following general formula:

    R.sup.1 SO.sub.n --CH═CH--CONR.sup.3 R.sup.4

wherein R¹, R³ and R⁴ are the same as in formula (1) and n=1 or 2.

EXAMPLE 1

0.50 mol of sodium hydroxide was dissolved in 500 ml of water. 0.55 mol of acetylene monocarboxylic acid was added thereto in dropwise fashion. 0.50 mol of lauryl mercaptan was then added at room temperature. After completion of the dropwise addition, the mixture was agitated at room temperature for 3 hours. The reaction mixture was neutralized with dilute hydrochloric acid and extracted with benzene to obtain a crystalline compound, the yield being 93% based on the amount of the starting mercaptan. The obtained crystalline compound was subjectd to infrared analysis (IR), nuclear magnetic resonance analysis (NMR), and elementary analysis. The results of the analyses are shown as follows:

IR:1660 (C═O) CM⁻¹.

NMR (CCl₄, TMS):δ 7.25 (doublet, 1H, ═CH--COO), 5.85 ppm (doublet, 1H, --S--CH═).

Result of the elementary analysis:

    ______________________________________                                                   found       calcd.                                                   ______________________________________                                         C (%)       66.3          66.1                                                 H (%)       10.3          10.4                                                 ______________________________________                                    

From the results of the above analyses, the above crystallized compound was identified as having the following formula

    n--C.sub.12 H.sub.25 S--CH═CH--COOH

the sodium salt of the above compound having the formula:

    n--C.sub.12 H.sub.25 S--CH═CH--COONa

possesses excellent surfactant activity, and the CMC (critical micelle concentration) value thereof at 50° C. was 0.60 millimol concentration.

EXAMPLE 2

Various mercaptans were reacted with acetylene monocarboxylic acid. The reaction conditions and the yields are shown in Table 1, and the properties of the reaction products are shown in Table 2.

                                      Table 1:                                     __________________________________________________________________________     Preparation of β-sulfenyl acrylic acids                                          Quantity of acetylene                                                                      Sodium  Reac-                                                                              Reac-                                           Mercaptan                                                                             monocarboxylic acid                                                                        hydrox- tion                                                                               tion               Yield (%                     (R.sup.1 SH)                                                                          (mol) added to 0.50                                                                        ide  H.sub.2 O                                                                         temp.                                                                              period             based on                     R.sup.1                                                                               mol of mercaptan                                                                           (mol)                                                                               (ml)                                                                              (° C.)                                                                      (hr)                                                                               Product        mercaptan)                   __________________________________________________________________________     C.sub.4 H.sub.9                                                                       0.55        0.50 500                                                                               25  3   C.sub.4 H.sub.9 SCHCHCOOH                                                                     85                           C.sub.6 H.sub.13                                                                      0.55        0.50 500                                                                               25  3   C.sub.6 H.sub.13 SCHCHCOOH                                                                    82                           C.sub.8 H.sub.17                                                                      0.55        0.50 500                                                                               25  3   C.sub.8 H.sub.17 SCHCHCOOH                                                                    88                           C.sub.12 H.sub.25                                                                     0.55        0.50 500                                                                               25  3   C.sub.12 H.sub.25 SCHCHCOOH                                                                   93                           C.sub.14 H.sub.29                                                                     0.55        0.50 500                                                                               25  3   C.sub.14 H.sub.29 SCHCHCOOH                                                                   83                            ##STR3##                                                                             0.55        0.50 500                                                                               25  3                                                                                   ##STR4##      80                           C.sub.18 H.sub.35                                                                     0.55        0.50 500                                                                               25  3   C.sub.18 H.sub.35 SCHCHCOOH                                                                   83                           (oleyl)                                                                        CH.sub. 3                                                                             0.55        0.50 500                                                                               25  3   CH.sub.3 SCHCHCOOH                                                                            68                           C.sub.20 H.sub.41                                                                     0.55        0.50 500                                                                               25  3   C.sub.20 H.sub.41 SCHCHCOOH                                                                   72                           __________________________________________________________________________

                                      table 2:                                     __________________________________________________________________________     Properties of β-sulfenyl acrylic acids                                                                               Result of elementary analysis                             IR     NMR           found   calcd.                      Compound        Property                                                                             (cm.sup.-1)                                                                        (CCL.sub.4, TMS, δ ppm)                                                                   C (%)                                                                              H (%)                                                                              C (%)                                                                              H                       __________________________________________________________________________                                                            (%)                     C.sub.4 H.sub.9 SCHCHCOOH                                                                      mp.   1663                                                                               7.25(doublet,1H,CHCOO)                                                                          52.3                                                                               7.5 52.5                                                                               7.6                                     88°-89° C.                                                                 5.85(doublet,1H,SCH)                                                 (in hexane)                                                    C.sub.6 H.sub.18 SCHCHCOOH                                                                     86°-88° C.                                                             1660                                                                               7.21(doublet,1H,CHCOO)                                                                          57.1                                                                               8.3 57.4                                                                               8.6                                     (in hexane)                                                                              5.83(doublet,1H,SCH)                                 C.sub.8 H.sub.17 SCHCHCOOH                                                                     90°-93° C.                                                             1658                                                                               7.20(doublet,1H,CHCOO)                                                                          60.7                                                                               9.1 61.1                                                                               9.3                                     (in hexane)                                                                              5.65(doublet,1H,SCH)                                 C.sub.12 H.sub.25 SCHCHCOOH                                                                    92°-94° C.                                                             1660                                                                               7.24(doublet,1H,CHCOO)                                                                          66.3                                                                               10.3                                                                               66.1                                                                               10.4                                    (in hexane)                                                                              5.80(doublet,1H,SCH)                                 C.sub.14 H.sub.29 SCHCHCOOH                                                                    93°-95° C.                                                             1660                                                                               7.18(doublet,1HCHCOO)                                                                           67.8                                                                               10.9                                                                               68.0                                                                               10.7                                    (in hexane)                                                                              5.79(doublet,1H,SCH)                                  ##STR5##       110°-112° C. (in hexane)                                               1663                                                                               7.26(doublet,1H,CHCOO) 5.76(doublet,1H,SCH)                                                     60.3                                                                               4.4 60.0                                                                               4.5                     C.sub.18 H.sub.35 SCHCHCOOH                                                                    56°-57° C.                                                             1670                                                                               7.26(doublet,1H,CHCOO)                                                                          69.9                                                                               10.6                                                                               71.1                                                                               10.8                                    (in hexane)                                                                              5.60(doublet,1H,SCH)                                 CH.sub.3 SCHCHCOOH                                                                             liquid                                                                               1660                                                                               7.30(doublet,1H,CHCOO)                                                                          40.5                                                                               5.0 40.7                                                                               5.1                                               5.60(doublet,1H,SCH)                                 C.sub.20 H.sub.41 SCHCHCOOH                                                                    89°-90° C.                                                             1665                                                                               7.38(doublet,1H,CHCOO)                                                                          71.4                                                                               11.6                                                                               71.8                                                                               11.5                                              5.21(doublet,1H,SCH)                                 __________________________________________________________________________

example 3

0.30 mol of β-lauryl sulfenyl acrylic acid synthesized in Example 1 was dissolved in 200 ml of CCl₄. 0.45 mol of SOCl₂ was added to the obtained solution dropwise at room temperature and the solution was agitated at room temperature for 1 hour. CCl₄ and excess SOCl₂ were then removed under reduced pressure, and a viscous liquid was obtained at a yield of 92%. The results of the analyses of the liquid were as follows:

IR:1775 (C═O) cm⁻¹.

NMR (CCl₄, TMS):δ 7.20 (doublet, 1H, ═CH--COCl) 5.78 ppm (doublet, 1H, --S--CH═)

Result of the elementary analysis:

    ______________________________________                                                   found       calcd.                                                   ______________________________________                                         C (%)       61.7          61.9                                                 H (%)       9.6           9.4                                                  ______________________________________                                    

From the results of the above analyses, the above viscous liquid was identified as having the formula:

    n--C.sub.12 H.sub.25 S--CH═CH--COCl

EXAMPLE 4

Various halides of β-sulfenyl acrylic acid were synthesized. The reaction conditions and the yields are shown in Table 3.

                                      Table 3:                                     __________________________________________________________________________     Preparation of halides of β-sulfenyl acrylic acid                                                                                   Yield                                                                          based                Used β-   Quantity of halo-                          on β-           sulfenyl       genating agent  Reac-                                                                              Reac-                  sulfenyl             acrylic  Used halo-                                                                           (mol) added to  tion                                                                               tion                   acrylic              acid     genation                                                                             0.30 mol of β-sul-                                                                        temp.                                                                              period                 acid                 R.sup.1  agent fenyl acrylic acid                                                                      Solvent                                                                               (°C.)                                                                       (hr)  Product      State                                                                              (%)                  __________________________________________________________________________     C.sub.12 H.sub.25                                                                       SOCl.sub.2 0.45                                                                               (CCl.sub.4 (200ml)                                                                      25  1.0                  92                                       0.39         70  1.0                  68                            PCl.sub.3  0.45                                                                               (CCl.sub.4 (200ml)                                                                      25  1.5                  76                                       0.39         70  1.5                  62                                                            C.sub.12 H.sub.25 SCHCHCOCl                                                                 liquid                            PCl.sub.5  0.45                                                                               (CCl.sub.4 (200ml)                                                                      25  1.3                  83                                       0.39         70  1.3                  55                            POCl.sub.3 0.45                                                                               (CCl.sub.4 (200ml)                                                                      25  2.0                  64                                       0.39         70  2.0                  55                            PBr.sub.3  0.45                                                                               (CCl.sub.4 (200ml)                                                                      25  1.3                  83                                       0.39         70  1.3                  70                                                            C.sub.12 H.sub.25 SCHCHCOBr                                                                 liquid                            PBr.sub.5  0.45                                                                               (CCl.sub.4 (200ml)                                                                      25  1.3                  68                                       0.39         70  1.3                  62                    ##STR6##                                                                               SOCl.sub.2 PCl.sub.3 PCl.sub.5 POCl.sub.3                                                 0.45 0.39 0.45 0.39 0.45 0.39 0.45 0.39                                            (CCl.sub.4 (200ml) (CCl.sub.4 (200ml) (CCl.sub.4                               (200ml) (CCl.sub.4 (200ml)                                                              25 70 25 70 25 70 25 70                                                             1.0 1.0 1.5 1.5 1.3 1.3 2.0                                                      .0                                                                               PhSCHCHCOCl  liquid                                                                            80 62 74 72 63                                                                 60 74 68             Phenyl   PBr.sub.3  0.45                                                                               (CCl.sub.4 (200ml)                                                                      25  1.3                  80                                       0.39         70  1.3                  72                                                            PhSCHCHCOBr  liquid                            PBr.sub.5  0.45                                                                               (CCl.sub.4 (200ml)                                                                      25  1.3                  64                                       0.39         70  1.3                  55                   CH.sub.3 SOCl.sub.2 0.45                                                                               (CCl.sub.4 (200ml)                                                                      25  1.0                  88                                       0.39         70  1.0                  60                            PCl.sub.3  0.45                                                                               (CCl.sub.4 (200ml)                                                                      25  1.5                  70                                       0.39         70  1.5                  58                                                            CH.sub.3 SCHCHCOCl                                                                          liquid                            PCl.sub.5  0.45                                                                               (CCl.sub.4 (200ml)                                                                      25  1.3                  63                                                                                2                                     0.39         70  1.3                  60                            POCl.sub.3 0.45                                                                               (CCl.sub.4 (200ml)                                                                      25  2.0                  80                                       0.39         70  2.0                  61                            PBr.sub.3  0.45                                                                               (CCl.sub.4 (200ml)                                                                      25  1.3                  75                                       0.39         70  1.3                  60                                                            CH.sub.3 SCHCHCOBr                                                                          liquid                            PBr.sub.5  0.45                                                                               (CCl.sub.4 (200ml)                                                                      25  1.3                  68                                       0.39         70  1.3                  55                   C.sub.20 H.sub.41                                                                       SOCl.sub.2 0.45                                                                               (CCl.sub.4 (200ml)                                                                      25  1.0                  75                                       0.39         70  1.0                  55                            PCl.sub.3  0.45                                                                               (CCl.sub.4 (200ml)                                                                      25  1.5                  68                                       0.39         70  1.5                  48                                                            C.sub.20 H.sub.41 SCHCHCOCl                                                                 liquid                   C.sub.20 H.sub.41                                                                       PCl.sub.5  0.45                                                                               (CCl.sub.4 (200ml)                                                                      25  1.3                  75                                       0.39         70  1.3                  62                            POCl.sub.3 0.45                                                                               (CCl.sub.4 (200ml)                                                                      25  2.0                  66                                       0.39         70  2.0                  48                            PBr.sub.3  0.45                                                                               (CCl.sub.4 (200ml)                                                                      25  1.3                  55                                       0.39         70  1.3                  38                                                            C.sub.20 H.sub.41 SCHCHCOBr                                                                 liquid                            PBr.sub.5  0.45                                                                               (CCl.sub.4 (200ml)                                                                      25  1.3                  64                                       0.39         70  1.3                  32                   Oleyl    SOCl.sub.2 0.45                                                                               (CCl.sub.4 (200ml)                                                                      25  1.0                  80                   (C.sub.18 H.sub.35)                                                                                0.39         70  1.0                  61                            PCl.sub.3  0.45                                                                               (CCl.sub.4 (200ml)                                                                      25  1.5                  63                                       0.39         70  1.5                  33                                                            C.sub.18 H.sub.35 SCHCHCOCl                                                                 liquid                            PCl.sub.5  0.45                                                                               (CCl.sub.4 (200ml)                                                                      25  1.3                  75                                       0.39         70  1.3                  60                            POCl.sub.3 0.45                                                                               (CCl.sub.4 (200ml)                                                                      25  2.0                  63                                       0.39         70  2.0                  33                            PBr.sub.3  0.45                                                                               (CCl.sub.4 (200ml)                                                                      25  1.3                  81                                       0.39         70  1.3                  70                                                            C.sub.18 H.sub.35 SCHCHCOBr                                                                 liquid                            PBr.sub.5  0.45                                                                               (CCl.sub.4 (200ml)                                                                      25  1.3                  63                                       0.30         70  1.3                  60                   __________________________________________________________________________

EXAMPLE 5

0.3 mol of β-lauryl sulfenyl acrylic acid synthesized in Example 1 and 0.75 mol of diethanol amine were heated at 170° C. for 3 hours, and the formed water was distilled off. The reaction mixture was then poured into 300 ml of water, and extracted with diethyl ether to obtain a viscous liquid at a yield of 65%.

The results of the analyses of the obtained liquid are set forth below.

IR: (1630 (cm⁻¹).

NMR (CCl₄, TMS): δ 7.30 (doublet, 1H, ═CH--CON), 5.90 ppm (doublet, 1H, --S--CH═)

Result of the elementary analysis:

    ______________________________________                                                   found       calcd.                                                   ______________________________________                                         C (%)       63.3          63.5                                                 H (%)       10.3          10.4                                                 ______________________________________                                    

From the results of the above analyses, the above liquid was identified as having the formula: ##STR7##

EXAMPLE 6

1.5 mols of dimethyl amine was dissolved in 100 ml of pyridine. 0.30 mol of chloride of β-lauryl sulfenyl acrylic acid synthesized in Example 3 was added in drops to the solution. The reaction mixture was agitated at 25° C. for 1 hour. The reaction mixture was then poured into 200 ml of water and extracted with diethyl ether to obtain a liquid at a yield of 82%.

The results of the analyses of the above liquid are set forth below.

IR: 1635 (cm⁻¹).

NMR (CCl₄, TMS): δ 7.25 (doublet, 1H, ═CH--CON--), 5.93 ppm (doublet, 1H, --S--CH═)

Result of the elementary analysis:

    ______________________________________                                                   found       calcd.                                                   ______________________________________                                         C (%)       68.4          68.1                                                 H (%)       10.9          11.1                                                 ______________________________________                                    

From the results of the above analyses, the above liquid was identified as having the formula: ##STR8##

EXAMPLE 7

0.6 mol of taurine (NH₂ CH₂ CH₂ OSO₂ Na) and 0.6 mol of Na₂ CO₃ were dissolved in 200 ml of water. 0.3 mol of β-lauryl sulfenyl acrylic chloride synthesized in Example 3 was added to the solution and reacted at 25° C. for 1 hour. Water was removed from the reaction mixture. The fraction which is soluble in isopropyl alcohol was then concentrated to obtain a crystallized compound. The results of the analyses of the crystallized compound are set forth below.

IR: 1630 (cm⁻¹).

NMR (CD₃ OD), TMS): δ 7.20 (doublet, 1H, ═CH--CON--), 5.91 ppm (doublet, 1H, --S--CH═)

Result of the elementary analysis:

    ______________________________________                                                   found       calcd.                                                   ______________________________________                                         C (%)       50.5          50.8                                                 H (%)       7.8           8.0                                                  ______________________________________                                    

From the results of the above analyses, the above crystallized compound was identified as having the formula:

    n--C.sub.12 H.sub.25 S--CH═CH--CONHCH.sub.2 CH.sub.2 SO.sub.3 Na

EXAMPLE 8

Various β-sulfenyl acrylic amides were prepared. The reaction conditions and the yields are shown in Table 4, and the properties of the formed substances are shown in Table 5.

    Table 4:       Preparation of β-sulfenyl acrylic amides   Quantity of     Yield      (R.sup.3 R.sup.4 NH)     based   (mol) added  Reac- Reac-  the used Used      com- Used to 0.30 mol  tion tion  compound pound (4) amine of the used      temp. period  (4) R.sup.1 ; Y; R.sup.3 R.sup.4 NH: compound (4) Solvent      (°C.) (hr) Product (%)                 C.sub.12       H.sub.25 Cl      ##STR9##       1.5 pyridine(100ml) 25 1       ##STR10##       82 C.sub.12       H.sub.25 OH      ##STR11##       1.5 -- 170        3      ##STR12##       65 C.sub.12       H.sub.25 Cl      ##STR13##       0.6 Na.sub.2 CO.sub.3 (0.6mol)N.sub.2 O(200ml) 50 1 C.sub.12 H.sub.25      SCHCHCONHCH.sub.2 CH.sub.2 SO.sub.3       Na 72      ##STR14##       Cl       ##STR15##       1.5 pyridine(100ml) 25 1       ##STR16##       68 Ph OH       ##STR17##       1.5 -- 170        3      ##STR18##       65 Ph Cl       ##STR19##       0.6 Na.sub.2 CO.sub.3 (0.6mol)H.sub.2 O(200ml) 50 1 PhSCHCHCONHCH.sub.2      CH.sub.2 SO.sub.3       Na 53 CH.sub.3 Cl      ##STR20##       1.5 pyridine(100ml) 25 1       ##STR21##       63 CH.sub.3 OH       ##STR22##       1.5 -- 170        3      ##STR23##       55 CH.sub.3 Cl       ##STR24##       0.6 Na.sub.2 CO.sub.3 (0.6mol)H.sub.2)(200ml) 50 1 CH.sub.3       SCHCHCONHCH.sub.2 CH.sub.2 SO.sub.2 Na.sub.3 72 C.sub.20 H.sub.41 Cl       ##STR25##       1.5 pyridine(100ml) 27 1       ##STR26##       64 C.sub.20       H.sub.41 OH      ##STR27##        1.5 -- 170        3      ##STR28##       53 C.sub.20       H.sub.41 Cl      ##STR29##       0.6 Na.sub.2 CO.sub.3 (0.6mol)H.sub.2 O(200ml) 50 1 C.sub.20 H.sub.41      SCHCHCONHCH.sub.2 CH.sub.2 SO.sub.3 Na 70 Oleyl(C.sub.18 H.sub.35) Cl       ##STR30##       1.5 pyridine(100ml) 25 1       ##STR31##       83  OH       ##STR32##       1.5 -- 170        3      ##STR33##       76  Cl       ##STR34##       0.6 Na.sub.2 CO.sub.3 (0.6mol)H.sub.2 O(200ml) 50 1 C.sub.18 H.sub.35      SCHCHCONHCH.sub.2 CH.sub.2 SO.sub.3       Na 63

    Table 5       Properties of β-sulfenyl acrylic amides Results of elementary      analysis found calcd. Compound Property IR(cm.sup.-1) NMR(CCl.sub.4      TMS,∂,ppm) C(%) H(%) C(%) H(%)       ##STR35##       liquid 1635(CON) 7.25(doublet,1H,CHCON)5.93(doublet,1H,SCH) 68.4 10.9      68.1 11.1       ##STR36##       liquid 1630(CON) 7.30(doublet,1H,CHCON)5.90(doublet,1H,SCH) 63.3 10.3      63.5 10.4  m.p. C.sub.12 H.sub.25 SCHCHCONHCH.sub.2 CH.sub.2 SO.sub.3 Na      110°-115° C. 1630 7.20(doublet,1H,CHCON) 50.5 7.8 50.8 8.0       (from isopro- (CON) 5.91(doublet,1H, SCH)  alcohol)  [CD.sub.3 OD,TMS]       ##STR37##       liquid 1632 (CON) 7.30(doublet,1H,CHCON)5.89(doublet,1H,SCH) 63.7 6.1      63.8 6.3       ##STR38##       liquid 1630(CON) 7.26(doublet,1H,CHCON)5.91(doublet,1H,SCH) 58.7 6.3      58.4 6.4  m.p. PhSCHCHCONCH.sub.2 CH.sub.2 SO.sub.3       Na 120°-123° C. 1628 7.24(doublet,1H,CHCON) 42.5 4.3 42.7      3.9  from isopro- (CON) 5.92(doublet,1H, SCH)  pyl alcohol  [CD.sub.3      OD, TMS]       ##STR39##       liquid 1630(CON) 7.20(doublet,CHCON)5.86(doublet,SCH) 49.3 7.4 49.6 7.6       ##STR40##       liquid 1628(CON) 7.23(doublet,CHCON)5.92(doublet,SCH) 46.9 47.4 46.8      7.4  m.p. CH.sub.3 SCHCHCONHCH.sub.2 CH.sub.2 SO.sub.3       Na 120°-121° C. 1629 7.18(doublet, CHCON) 29.3 4.1 29.1      4.0  (from isopro- (CON) 5.95 doublet,SCH) pyl alcohol)  [inCD.sub.3 OD]       ##STR41##       liquid 1631(CON) 7.26(doublet,CHCON)5.73(doublet,SCH) 72.6 11.8 72.9      12.0       ##STR42##       liquid 1630(CON) 7.19(doublet,CHCON)5.84(doublet,SCH) 68.5 11.3 68.7      11.3  m.p. C.sub.20 H.sub.41 SCHCHCONHCH.sub.2 CH.sub.2 SO.sub.3 Na      130°-131° C. 1630 7.62(doublet,CHCON) 59.3 9.2 59.4 9.1      (from isopro- (CON) 5.33(doublet, SCH)  pyl alcohol)  [inCD.sub.3 OD]       ##STR43##       liquid 1630(CON) 7.82(doublet,CHCON)5.34(doublet,SCH) 74.2 8.8 74.4 9.0       ##STR44##       liquid 1628(CON) 7.53(doublet,CHCON)5.76(doublet,SCH) 73.5 11.4 73.3      11.6  m.p. C.sub.18 H.sub.35 SCHCHCONHCH.sub.2 CH.sub.2 SO.sub.3 Na      120°-121° C. 1630 7.24(doublet, CHCON) 57.4 8.6 57.1 8.7      from isopro- CON) 5.86(doublet,SCH)  pyl alcohol)  [inCD.sub.3 OD]

EXAMPLE 9

This Example shows the list of compounds having antibiotic activities and the growth preventing effects thereof against the organisms positive to and negative to Gram's staining.

In accordance with the test method using agar culture media mixed with the compounds, the concentrations of compounds necessary for preventing growth of various organisms were determined.

1 ml of a solution of each of the compounds having predetermined concentration as set forth in the following Tables 6 and 7 was put on a Petri dish, and 19 ml of Sabouraud's agar culture medium preliminarily heated to be a molten state was then added to and uniformly mixed with the above solution, and the mixture was allowed to cool and solidify. One platinum loop of an organism solution containing one million cells of organism per 1 ml was coated on the surface of the solidified culture medium, and cultivated for 72 hours in a thermostatic chamber maintained at 30° C. The state of growth of the organism on each culture medium after cultivation was observed, and the minimum concentration of the respective compounds necessary to be contained in each of the culture medium was determined.

                                      Table 6                                      __________________________________________________________________________     Minium Conc. for Preventing Growth (ppm)                                                            Staphylocuccus aureas                                                                       Bacillus subtilis                            Compound             1000 500  100                                                                               1000                                                                              500                                                                               100                                    __________________________________________________________________________     n-C.sub.4 H.sub.9SCHCHCON(CH.sub.2 CH.sub.2 OH).sub.2                                               -    ± +  -  +  +                                       ##STR45##           -    -    -  -  -  ±                                    ##STR46##           -    -    +  -  -  +                                      n-C.sub.7 H.sub.15 CON(CH.sub.2 CH.sub.2 OH).sub.2                                                  -    +    +  -  +  +                                      (Reference)                                                                     ##STR47##           -    -    +  -  ±                                                                              +                                      __________________________________________________________________________      (Note)-                                                                        + : Growth was observed; Growth preventing effect was not found.               ± : Growth was observed to some extent; Growth preventing effect was        found to an appreciable extent.                                                --  : Growth was not observed; Perfect growth preventing effect is found.

    Table 7       Minimum Conc. for Preventing Growth Staphylococcus  Escherichia      Pseudomona aureus Bacillus subtilis coli Proteus vulgaris aeruginosa      Compounds 1000 500 100 1000 500 100 1000 500 100 1000 500 100 1000 500      100       ##STR48##       - - - - - - - ± + --+-++       ##STR49##       - - - - - ± - + + -+++++       ##STR50##       - - - - - + - + + ±+++++       ##STR51##       - - - - + + ± + + ++++++       ##STR52##       - - - - - - - + + -++±++       ##STR53##       - - + - - + + + + ++++++ n-C.sub.10 H.sub.32SCHCHCON(CH.sub.2 CH.sub.2      OH).sub.2 - + + - + + + + + + +++++ n-C.sub.4 H.sub.9SCH CHCONH.sub.2 -      - + - + + + + + + + + + + +       ##STR54##       - - - - - - - ± + -±+-++       ##STR55##       - - + - - + - + + -++±++       ##STR56##       - - - - - - - + + - - ± - + +       ##STR57##       - - - - - - - ± + -- +-++       ##STR58##       - - - - - + - + + ±++ + ++       ##STR59##       - - + - - + + + + ++++++       ##STR60##       - + + - ± + + + + ++++++ (Reference)       ##STR61##       - + + - + + ± + + ± + + + + +       ##STR62##       - - + - ± + - ± + - - + ± + +

EXAMPLE 10 (Fungicidal Activity Test to Helminthosporium Oryzae)

In synthetic resin pots having a length of 16 cm, a width of 10 cm and a depth of 5 cm, there were placed twenty rice stubbles which had been cultivated in a hothouse until they grew to the four leaves stage. Then twenty ml of an aqueous solution containing 500 ppm of a test compound was sprayed onto the rice plants in each of the pots. A control sample of rice stubble was not treated with any test compound. The rice plants were allowed to stand for one day in the hothouse after the spraying. Then an aqueous dispersion of the fruit bodies of Helminthosporium Oryzae virus was sprayed and inoculated uniformly onto the rice plants. The fruit bodies had been obtained by culturing in a test tube. Then, each pot having the inoculated rice plants was placed into a thermostat tank maintained at 27° C. and a relative humidity of 95 or more percent in order that the rice plants might be infected. Five days after the plants were infected with the virus, the affected spots on each leaf were observed and the fungicidal activity was calculated in comparison with the observation of affected areas of the control sample on which the test compound had not been sprayed. The fungicidal activity was calculated from the following formula: ##EQU1## in which Y is the number of affected spots per one treated leaf and X is the number of affected spots per one control leaf. The results are shown in Table 8. The test compounds did not otherwise have a bad effect on the growth of the plants.

                  Table 8                                                          ______________________________________                                                                Concen-                                                                        tration   Fungi-                                                               of Test   cidal                                                                Compound  activity                                      Compound               (ppm)     (%)                                           ______________________________________                                         CH.sub.3 SCHCHCONH.sub.2                                                                              500       53                                             ##STR63##             500       48                                             ##STR64##             500       47                                             ##STR65##             500       50                                            C.sub.2 H.sub.5 SCHCHCONH.sub.2                                                                       500       62                                             ##STR66##             500       60                                            n-C.sub.4 H.sub.9 SCHCHCONH.sub.2                                                                     500       64                                             ##STR67##             500       58                                             ##STR68##             500       62                                             ##STR69##             500       65                                            n-C.sub.6 H.sub.13 SCHCHCONH.sub.2                                                                    500       63                                             ##STR70##             500       67                                            n-C.sub.6 H.sub.13 SO.sub.2 CHCHCONH.sub.2                                                            500       57                                            n-C.sub.8 H.sub.17 SCHCHCONH.sub.2                                                                    500       73                                             ##STR71##             500       82                                             ##STR72##             500       76                                             ##STR73##             500       90                                            n-C.sub.10 H.sub.21 SO.sub.2 CHCHCON(CH.sub.2 CH.sub.2 OH).sub.2                                      500       81                                             ##STR74##             500       88                                             ##STR75##             500       95                                            n-C.sub.12 H.sub.25 SOCHCHCONHCH.sub.2 CH.sub.2 SO.sub.3 Na                                           500       91                                             ##STR76##             500       92                                            n-C.sub.12 H.sub.25 SCHCHCONHCH.sub.2 CH.sub.2 COONa                                                  500       87                                            ______________________________________                                    

EXAMPLE 11 (Fungicial Activity Test to Colletorichum Lagenarium)

Twenty ml of a liquid agent containing 500 ppm of a test compound was sprayed on a cucumber plant planted in a pot. On the next day, a liquid dispersion of fruit bodies of Colletorichum Lagenarium was sprayed with a microsprayer and inoculated on the cucumber in an inoculating box maintained at 27° C. and a relative humidity of 95 or more percent. Two days after the inoculation, each pot was placed in a hothouse and seven days thereafter the affected spots that had appeared on the leaf were observed. The fungicidal activity was calculated in the same manner as in Example 10. The results are shown in Table 9.

                                      Table 9                                      __________________________________________________________________________                                Concentration of Test                                                                     Fungicidal                                                          Compound   activity                                 Test Compound              (ppm)      (%)                                      __________________________________________________________________________     CH.sub.3 SCHCHCONH.sub.2   500        49                                        ##STR77##                 500        53                                        ##STR78##                 500        55                                       C.sub.2 H.sub.5 SCHCHCONH.sub.2                                                                           500        60                                        ##STR79##                 500        63                                        ##STR80##                 500        70                                       n-C.sub.4 H.sub.9 SO.sub.2 CHCHCONH.sub.2                                                                 500        72                                        ##STR81##                 500        75                                        ##STR82##                 500        82                                        ##STR83##                 500        80                                        ##STR84##                 500        85                                       n-C.sub.8 H.sub.17 SOCHCHCON(CH.sub.2 CH.sub.2 OH).sub.2                                                  500        79                                        ##STR85##                 500        92                                       n-C.sub.10 H.sub.21 SCHCHCONHCH.sub.2 CH.sub.2 SO.sub.3 Na                                                500        87                                       n-C.sub.12 H.sub.25 SCHCHCONH.sub.2                                                                       500        100                                       ##STR86##                 500        100                                       ##STR87##                 500        98                                        ##STR88##                 500        89                                       n-C.sub.16 H.sub.33 SCHCHCONH.sub.2                                                                       500        91                                        ##STR89##                 500        88                                       __________________________________________________________________________

The sulfenyl and sulfonyl compounds having the formula R¹ SO_(n) --CH═CH--COX, wherein R¹ and X are the same as in formula (1) and n is one or 2, are described in Japanese Patent Applications Ser. No. 84707/75, filed July 10, 1975, and Ser. No. 84946/75, filed July 11, 1975, corresponding to U.S. Ser. No. 702,405, filed July 6, 1976, the entire contents of which are incorporated herein by reference.

The compounds of the invention, and the sulfinyl and sulfonyl derivatives thereof, possess antimicrobial activity against one or more of bacteria, fungi and yeasts. They can be used as preservatives and antiseptics in cosmetic oils, lotions and creams, and pharmaceutical oil, lotion and cream compositions for topical application. They can be used in place of the preservatives and antiseptics conventionally used in such compositions, at approximately the same concentration levels. In particular, they can be used in place of sodium salicylate, ethyl paraben, potassium sorbate and anhydrous sodium acetate, which are conventional preservatives, in prior art compositions that employ those conventional preservatives. 

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
 1. A compound having the formula ##STR90## wherein R¹ is alkyl having 6 to 20 carbon atoms; and wherein R³ and R⁴, which can be the same or different, are hydrogen, unsubstituted alkyl having 1 to 6 carbon atoms or hydroxy-substituted alkyl having 2 to 6 carbon atoms.
 2. A compound according to claim 1, wherein R¹ is alkyl having at least 8 carbon atoms.
 3. A compound according to claim 2, wherein R¹ is straight chain alkyl.
 4. A compound according to claim 2 in which ##STR91## is --NH₂.
 5. A compound according to claim 2 in which ##STR92## is --N(CH₃)₂.
 6. A compound according to claim 2 in which ##STR93## is --N(C₂ H₅)₂.
 7. A compound according to claim 2 in which ##STR94## is --NH(CH₂ CH₂ CH₃).
 8. A compound according to claim 2 in which ##STR95## is --N(CH₂ CH₂ OH)₂.
 9. A compound according to claim 1, having the formula

    n--C.sub.16 H.sub.33 SCH═CHCONH.sub.2.


10. A compound according to claim 1, having the formula

    n--C.sub.14 H.sub.29 SCH═CHCON(C.sub.2 H.sub.5).sub.2.


11. A compound according to claim 1, having the formula ##STR96##
 12. A compound according to claim 1, having the formula

    n--C.sub.12 H.sub.25 SCH═CHCONH.sub.2.


13. A compound according to claim 1, having the formula

    n--C.sub.10 H.sub.21 SCH═CHCON(CH.sub.3).sub.2.


14. A compound according to claim 1, having the formula ##STR97##
 15. A compound according to claim 1, having the formula

    n--C.sub.12 H.sub.25 SCH═CHCON(CH.sub.3).sub.2.


16. A compound according to claim 1, having the formula

    n--C.sub.8 H.sub.17 SCH═CHCON(CH.sub.3).sub.2.


17. A compound according to claim 1, having the formula

    n--C.sub.8 H.sub.17 SCH═CHCONH.sub.2.


18. A compound according to claim 1 wherein R¹ is alkyl having 8 to 12 carbon atoms. 